CN101367525A - Sodium calcium silicate biological material, preparation method and uses thereof - Google Patents

Sodium calcium silicate biological material, preparation method and uses thereof Download PDF

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Publication number
CN101367525A
CN101367525A CNA2008102001728A CN200810200172A CN101367525A CN 101367525 A CN101367525 A CN 101367525A CN A2008102001728 A CNA2008102001728 A CN A2008102001728A CN 200810200172 A CN200810200172 A CN 200810200172A CN 101367525 A CN101367525 A CN 101367525A
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calcium silicate
sodium calcium
powder
biological material
casio
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CN101367525B (en
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宁聪琴
赵迎珂
常江
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a calcium sodium silicate biological material, a preparation method thereof and the application thereof, which is characterized in that ethyl orthosilicate, water, sodium nitride or sodium chloride and tetra-nitric hydrate or calcium chloride are adopted as the raw materials; pure calcium sodium silicate (Na2CaSiO4) powder is synthesized in the sol-gel way; the powder is formed and sintered to be the ceramic of the calcium sodium silicate. After the calcium sodium silicate (Na2CaSiO4) powder or block material is steeped in the analog liquid, a silicon-rich layer is formed on the surface of the material, which can induce the generation of the hydroxylapatite. The ceramic of the calcium sodium silicate (Na2CaSiO4) can also induce the forming of the phosphorite. The calcium sodium silicate (Na2CaSiO4) has favorable biological peroperty, and is a potential biological active material, and can be used as the bone tissue engineering material, the bone stuffing material and the dental material.

Description

Sodium calcium silicate biological material, preparation method and its usage
Technical field
The present invention relates to a kind of sodium calcium silicate (Na of biologically active 2CaSiO 4) biomaterial, preparation method and its usage, belong to technical field of biological material.
Background technology
The bio-vitric of Si base and biological ceramics are being obtained significant success as the bone tissue engineer biomaterial in nearly decades, 58S for example, 77S etc.Outstanding feature is exactly that material surface forms rich Si layer and can induce the formation of hydroxyapatite and the propagation of stimulating osteoblast under the body fluid environment, has embodied biological activity preferably.The silicate ceramics that contained alkaline-earth metal ions in recent years has been subjected to extensive concern, for example akermanite (Ca 2MgSi 2O 7), combeite (Na 2Ca 2Si 3O 9) etc.Na is a kind of very active element and exists in a large number at human body, contain for example 45S5 bio-vitric of the bio-vitric of Na and biological ceramics, all commercializations and be applied to the clinical success that obtained such as Ceravital glass-ceramic, Bioverit biological ceramics etc. it is reported and contain sodium calcium silicate (Na 2CaSiO 4) glass-ceramic of crystalline phase has been applied to the tooth reparation.In addition, Na 2CaSiO 4Or one of principal crystalline phase of a kind of calcium phosphate silicon composite (silica-calcium phosphate composite) of El-Ghannam working group preparation.
So Na 2CaSiO 4Research as biomaterial has certain meaning with application, and the rarely seen report of its preparation.
Summary of the invention
The object of the present invention is to provide a kind of sodium calcium silicate biological material, preparation method and application thereof.Specifically, synthesize sodium calcium silicate (Na by sol-gel processing 2CaSiO 4) powder, sinter sodium calcium silicate (Na then into 2CaSiO 4) pottery; By the external biological activity, performance evaluations such as degradation property determine whether it has the ability as novel biological active materials.
Embodiment of the present invention is as follows:
Sodium calcium silicate (Na 2CaSiO 4) preparation of powder and block ceramic
(1) tetraethoxy and the volume ratio of 2mol/L ammonium nitrate 4-6:1 are mixed and are added about twice in the deionized water of tetraethoxy volume and about one times in the tetraethoxy volume of ethanol, make the nitrate that added afterwards to dissolve and to promote two-phase to dissolve each other, at room temperature fully stirred 30 minutes, make the abundant hydrolysis of tetraethoxy, add SODIUMNITRATE (or sodium-chlor) and calcium nitrate tetrahydrate (or calcium chloride) then, the mol ratio of its Na, Ca and Si is 2:1:1.Stir after 5-7 hour, sealing, ageing is 2-3 days in 60 ℃, obtain stable sol, and drying obtains gel in 120 ℃.
(2) dried xerogel was calcined 2-4 hour at 800 ℃, obtained sodium calcium silicate (Na 2CaSiO 4) powder.
(3) will obtain sodium calcium silicate (Na 2CaSiO 4) powder is at 1100 ℃ of calcinings 17 hours, in addition purifying.
(4) sodium calcium silicate (Na that synthesizing and purifying is crossed 2CaSiO 4) powder grinds, sieves, and polyvinyl alcohol (PVA) granulation of adding 6wt%, add-on is 5～10wt%, the dry-pressing sodium calcium silicate (Na under 5-10MPa of elder generation after the granulation 2CaSiO 4) the powder moulding, and isostatic cool pressing is handled under 150-300MPa.
(5) with the ceramic body that is pressed into 1000 ℃-1100 ℃ sintering 1-5 hour, can make sodium calcium silicate (Na 2CaSiO 4) pottery.
In sum, sodium calcium silicate biological material provided by the invention is pure sodium calcium silicate, and chemical formula is Na 2CaSiO 4, wherein the mol ratio of Na, Ca and Si is 2:1:1.
The biomaterial that is provided is powder shaped or block shape, and the size range of powder is 0.2 μ m～100 μ m, the relative volume density 85%～95% of block materials.
Sodium calcium silicate (Na 2CaSiO 4) powder and ceramic performance evaluation
1, sodium calcium silicate (Na 2CaSiO 4) powder and ceramic biological activity
Adopt simulated body fluid to soak sodium calcium silicate (Na 2CaSiO 4) powder and ceramic plate 1-7 days.Simulated body fluid contains ion identical with human plasma and ionic group concentration.It consists of:
NaCl： 7.996g/L
NaHCO 3： 0.350g/L
KCl： 0.224g/L
K 2HPO 4.3H 2O： 0.228g/L
MgCl 2.6H 2O： 0.305g/L
HCl： 1mol/L
CaCl 2： 0.278g/L
Na 2SO 4： 0.071g/L
NH 2C(CH 2OH) 3： 6.057g/L
After the immersion, the oven dry sample adopts XRD and SEM to detect the hydroxyapatite that forms.XRD result shows 3 days hydroxyapatites just attached to powder surface, and powder surface is just almost all covered by hydroxyapatite when soaking 7 days.The block that soaked 7 days in simulated body fluid is carried out SEM and EDS detection, and the ionic concn that detects solution simultaneously changes.Find that material surface has covered very thick one deck hydroxyapatite after 7 days, EDS result also illustrates has proved this point.In addition, power spectrum and the explanation of effects of ion concentration results, sodium calcium silicate (Na 2CaSiO 4) material induces hydroxyapatite to form by the rich Si layer of surperficial one deck in simulated body fluid, this serial experiment explanation sodium calcium silicate (Na 2CaSiO 4) material has good biological activity.
2, sodium calcium silicate (Na 2CaSiO 4) ceramic degradation property
With sodium calcium silicate (Na 2CaSiO 4) the ceramic degradation property that detects it over 1-28 days of in phosphate buffer soln PBS, soaking.PBS consists of:
KCl 0.2g/L
NaCl 8.0g/L
KH 2PO 4 0.2g/L
Na 2HPO 4·7H 2O 2.16g/L
Weight before ceramic plate soaks in addition is m0, and the quality after the immersion is mn, and rate of weight loss is:
(m 0-m n)/m 0×100％
The degradation process of weight-loss curve explanation pottery in PBS discharged by ion and effects of ion deposits two controlling factors at material surface, weightless maximum in the time of 14 days, then before 14 days degradation speed greater than sedimentation velocity, otherwise after 14 days.The sample that soaked 28 days is carried out the XRD test, and the result shows that there is the formation of phosphatic rock on the surface, has further proved sodium calcium silicate (Na 2CaSiO 4) good biological activity.
In view of the above, sodium calcium silicate (Na of the present invention 2CaSiO 4) material is a kind of novel biological activity bone renovating material.This material has good biology performance, can induce the formation of hydroxyapatite in simulated body fluid.In phosphate buffer soln progressively the degraded and the surface also can form phosphatic rock.This material property is superior, adopts the synthetic sodium calcium silicate (Na that forms more complicated of sol-gel processing 2CaSiO 4) method of material, it is fairly simple to have technology, and condition is easy to advantages such as control.
This shows sodium calcium silicate (Na provided by the invention 2CaSiO 4) after powder or block materials soaked in simulated body fluid, material surface formed one deck silicon-rich layer, can induce the generation of hydroxyapatite.This sodium calcium silicate (Na 2CaSiO 4) the ceramic formation that in phosphate buffer soln, also can induce phosphatic rock.Sodium calcium silicate (Na is described 2CaSiO 4) have good biological property, be a kind of very potential biological active materials.As engineering material of bone tissue, filling material of bone and dental material.
According to foregoing, not breaking away under this prerequisite of finding above-mentioned basic fundamental thought, according to the universal knowledege and the technique means of this area, to sodium calcium silicate (Na 2CaSiO 4) material adds other biological consistency and curative drug component, all belongs to modification, replacement and the change of the various ways that content of the present invention comprises, all belongs to scope of the present invention.
Description of drawings
Fig. 1 is sol-gel processing synthetic sodium calcium silicate (Na 2CaSiO 4) the powder XRD figure, as can be seen from the figure have only Na 2CaSiO 4(PDF 24-1069) peak exists, and does not have other impurity.
Fig. 2 is sodium calcium silicate (Na 2CaSiO 4) powder soaked simulated body fluid 1 day, the XRD figure of 3 days and 7 days.As can be seen from the figure generated hydroxyapatite.
Fig. 3 is sodium calcium silicate (Na 2CaSiO 4) the block ceramic SEM that soaks simulated body fluid (A figure), back (B figure) before 7 days schemes.Show sodium calcium silicate (Na 2CaSiO 4) the block ceramic surface coverage the thick hydroxyapatite layer of one deck.
Fig. 4 is sodium calcium silicate (Na 2CaSiO 4) block ceramic soak 7 days front and rear surfaces of simulated body fluid can spectrogram.
Fig. 5 is sodium calcium silicate (Na 2CaSiO 4) block ceramic soaked simulated body fluid 1 day, the ionic concn of solution variation after 3 days and 7 days.
Fig. 6 is sodium calcium silicate (Na 2CaSiO 4) 1 day-28 days weightlessness figure of block ceramic immersion PBS buffered soln.
Fig. 7 is sodium calcium silicate (Na 2CaSiO 4) XRD figure of block ceramic immersion PBS buffered soln after 28 days.The display material surface deposition phosphatic rock.
Embodiment
The invention will be further described below in conjunction with embodiment, but be not limited only to following examples.
Embodiment 1:
(1) tetraethoxy 24ml mixes with 6ml 2mol/L salpeter solution, add the deionized water of 20ml and the ethanol of 10ml, at room temperature fully stirred 20 minutes, adding 0.2 molar nitric acid sodium and 0.1 mole of calcium nitrate tetrahydrate then stirred 7 hours, sealing, ageing is 2 days in 60 ℃, and in 120 ℃ dry 3 days.
(2) drying is good xerogel obtains sodium calcium silicate (Na 800 ℃ of calcinings 2 hours 2CaSiO 4) powder.
Obtained powder is carried out X-ray diffraction analysis finds that prepared powder is pure sodium calcium silicate (PDF #24-1069) (as Fig. 1).
Embodiment 2:
(1) tetraethoxy 112ml and 2mol/L salpeter solution 20ml are mixed, and the ethanol of adding deionized water 200ml and 100ml, at room temperature fully stirred 30 minutes, adding 1 molar nitric acid sodium and 0.5 mole of calcium nitrate tetrahydrate then stirred 5 hours, sealing, ageing is 3 days in 60 ℃, and in 120 ℃ dry 3 days.
(2) drying is good xerogel obtains pure sodium calcium silicate (Na 1100 ℃ of calcinings 17 hours 2CaSiO 4) powder.
(3) ratio of synthetic powder in 1.5mg/ml immersed in the simulated body fluid, take out after 1 day, 3 days and 7 days and carry out X-ray diffraction analysis.Find that material surface is just covered by apatite layer after 3 days, material surface all is a phosphatic rock (Fig. 2) after 7 days.Show that institute's synthetic sodium calcium silicate powder has very high biological activity.
Embodiment 3:
(1) tetraethoxy 112ml and 2mol/L salpeter solution 20ml are mixed, and adding deionized water 200ml and 100ml ethanol, at room temperature fully stirred 30 minutes, adding 1 molar nitric acid sodium and 0.5 mole of calcium nitrate tetrahydrate then stirred 5 hours, sealing, ageing is 3 days in 60 ℃, and in 120 ℃ dry 3 days.
The xerogel that drying is good obtains pure sodium calcium silicate (Na 1100 ℃ of calcinings 17 hours 2CaSiO 4) powder.
(2) with synthetic powder ball milling, sieve after, and add the PVA solution granulation of 10wt%, (8MPa) dry-pressing becomes the disk shape sample of φ 10mm * 1mm, isostatic cool pressing under the 150Mpa condition again under the certain pressure.
(3) with disk shape sample 1100 ℃ of sintering 2 hours.Then agglomerating sodium calcium silicate ceramic plate is immersed and estimate its biological activity in the simulated body fluid.Use the variation of scanning electron microscopic observation specimen surface pattern and composition after 7 days, find that immersion was covered (Fig. 3) by spherical bone-like apatite stone granulate in sour sodium calcium ceramic plate surface after 7 days, power spectrum result and ionic concn result unite and are presented at ceramic surface and have formed one deck silicon-rich layer (Fig. 4 and Fig. 5) in addition, prove that the sodium calcium silicate pottery induces phosphatic rock to form by silicon-rich layer.
Embodiment 4:
(1) tetraethoxy 112ml and 2mol/L salpeter solution 20ml are mixed, and the ethanol of adding deionized water 200ml and 100ml, at room temperature fully stirred 30 minutes, adding 1 molar nitric acid sodium and 0.5 mole of calcium nitrate tetrahydrate then stirred 5 hours, sealing, ageing is 3 days in 60 ℃, and in 120 ℃ dry 3 days.The xerogel that drying is good obtains pure sodium calcium silicate (Na 1100 ℃ of calcinings 17 hours 2CaSiO 4) powder.
(2) with synthetic powder ball milling, sieve after, and add the PVA solution granulation of 6wt%, (5MPa) dry-pressing becomes the disk shape sample of φ 10mm * 1mm under the certain pressure.And then under the 200Mpa condition isostatic cool pressing.
(3) with the disk shape sample of step (2) 1100 ℃ of sintering 2 hours.Then agglomerating sodium calcium silicate ceramic plate is immersed and estimate its external degradation performance in the phosphate buffered saline buffer, weigh its degradation rate with rate of weight loss.The degraded of weight-loss curve explanation pottery in PBS discharged by ion and effects of ion deposits two process control at material surface, and be weightless maximum in the time of 14 days, and preceding 14 days degradation speeds are greater than sedimentation velocity, and the anti-deposition process of ionic is accelerated (Fig. 6) after 14 days.The sample that soaked 28 days is carried out the XRD test, and the result shows that there is the formation (Fig. 7) of phosphatic rock on the surface, has further proved sodium calcium silicate (Na 2CaSiO 4) good biological activity.

Claims (10)

1. sodium calcium silicate biological material is characterized in that chemical formula is pure Na 2CaSiO 4, the mol ratio of Na, Ca and Si is 2:1:1; Described sodium calcium silicate material is powder shaped or three-dimensional block shape.
2. by the described sodium calcium silicate biological material of claim 1, the particle diameter that it is characterized in that described Powdered sodium calcium silicate is 0.2～100 μ m.
3. by the described sodium calcium silicate biological material of claim 1, the relative volume density that it is characterized in that described block sodium calcium silicate is 85%～98%.
4. the method for preparing sodium calcium silicate biological material as claimed in claim 1 is characterized in that adopting sol-gel method synthetic silicic acid sodium calcium powder;
A. powder shaped sodium calcium silicate biological material:
(1) tetraethoxy is mixed and add deionized water and ethanol mixing with ammonium nitrate by the volume ratio of 4-6:1, stir and make the abundant hydrolysis of tetraethoxy;
(2) add SODIUMNITRATE and calcium nitrate tetrahydrate, the mol ratio of Na, Ca and Si is 2:1:1, stirs, seals and ageing acquisition stable sol;
(3) 120 ℃ of dryings of stable sol of step 2 gained are made gel;
(4) dried gel is obtained the sodium calcium silicate powder 800 ℃ of calcinings;
Or (5) calcine purifying with the sodium calcium silicate powder that step 4 obtains at 1100 ℃;
B. the preparation of block sodium calcium silicate:
(1) tetraethoxy is mixed and add deionized water and ethanol mixing with ammonium nitrate by the volume ratio of 4-6:1, stir and make the abundant hydrolysis of tetraethoxy;
(2) add SODIUMNITRATE and calcium nitrate tetrahydrate, the mol ratio of Na, Ca and Si is 2:1:1, stirs, seals and ageing acquisition stable sol;
(3) stable sol 120 dryings of step 2 gained are made gel;
(4) dried gel is obtained the sodium calcium silicate powder in 800 calcinings;
(5) the sodium calcium silicate powder that step 4 is obtained is at 1100 calcining purifying;
(6) Na behind step 5 purifying 2CaSiO 4Powder grind, sieve and add mass percent be 6% polyvinyl alcohol solution granulation, dry-pressing formed after again isostatic cool pressing handle, make ceramic body;
(7) ceramic body that step 6 is made is made Na in 1000-1100 ℃ of sintering 2CaSiO 4Powder.
5. by the preparation method of the described sodium calcium silicate biological material of claim 4, it is characterized in that described in the step 1. the deionized water of adding be 2 times of tetraethoxy volume, the ethanol of adding is 1 times of tetraethoxy volume.
6. by the preparation method of the described sodium calcium silicate biological material of claim 4, the concentration that it is characterized in that ammonium nitrate in the step 1 is 2mol/L; The polyvinyl alcohol solution add-on is a mass percent 6～10% during granulation.
7. by the preparation method of the described sodium calcium silicate biological material of claim 4, it is characterized in that the temperature of ageing described in the step 2 is 60 ℃, the time is 2-3 days; Churning time is 5-7 hour.
8. by the preparation method of the described sodium calcium silicate biological material of claim 4, it is characterized in that the calcination time described in the step 4 is 2-4 hour.
9. by the preparation method of the described sodium calcium silicate biological material of claim 4, it is characterized in that the dry-pressing formed pressure 5-10MPa described in the step 6, follow-up isostatic cool pressing pressure is 150-300MPa; The ceramic body sintering time is 1-5 hour in the step 7.
10. the application of the described sodium calcium silicate biological material of claim 1 is characterized in that being used for engineering material of bone tissue, filling material of bone or dental material.
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